Sergey K. Feducovich

Stereoselective electrochemical transformation of alkylidenecyanoacetates and malonate into (E)-3-substituted-2-cyanocyclopropane-1,1,2-tricarboxylates

Abstract Electrolysis of malonate and alkylidenecyanoacetates in alcohols in the presence of sodium bromide in an undivided cell results in the stereoselective formation of (E)-3-substituted 2-cyanocyclopropane-1,1,2-tricarboxylates in 75–85% yields.

ELECTROCHEMICAL CYCLODIMERIZATION OF ALKYLIDENEMALONATES

Abstract Electrolysis of dimethyl alkylidenemalonates RCH = C(COOMe)2 (R = n−Alk, Ph) in an undivided cell in MeOH in the presence of alkali metal halide as mediator, leads to the formation of cyclic dimers, i.e., 3,4-disubstituted 1,1,2,2-cyclobutanetetracarboxylates. The reaction proceeds via the reductive coupling of two substrate molecules at cathode and the cyclization of a hydrodimer dianion by its interaction with an active form of a mediator, an anode-generated halogen.

Indirect electrochemical oxidation of cyclic ketones: Influence of ring size, mediator and supporting electrolyte on the result of the reaction

Abstract The result of the indirect electrochemical oxidation of cyclic ketones in methanol in an undivided cell in the presence of sodium halides depends on the ring size of ketone and the type of mediator. Selectivity of the reaction in some cases and current efficiency are increased by addition of supporting electrolyte - sodium hydroxide. Formation of cyclic 2,2-dimethoxycycloalkanols and the electrochemically induced Favorskii rearrangement with the formation of methyl cycloalkencarboxylates containing in the ring one carbon atom less than starting ketone are the main ways of the indirect electrochemical oxidation of cyclic ketones.

Electrochemical Cyclodimerization of Alkylidenemalonates into 3,4-Disubstituted Cyclobutane-1,1,2,2-Tetracarboxylates

Abstract Alkylidenemalonates being electrolyzed in methanol in undivided cell with glassy carbon, carbon or lead cathode in the presence of sodium iodide or sodium bromide are transformed into 3,4-disubstituted cyclobutane-1,1,2,2-tetracarboxylates.

Indirect Electrochemical Oxidation of Aryl Alkyl Ketones Mediated by NaI–NaOH System: Facile and Effective Way to α-Hydroxyketals

Abstract Indirect electrochemical oxidation of aryl alkyl ketones in methanol in an undivided cell in the presence of sodium iodide–sodium hydroxide leads to the corresponding α-hydroxyketals in 75–85% substance yield (70–75% current yield).

Indirect electrochemical oxidation of aliphatic ketones mediated by the NaI–NaOH system:a facile way to unsaturated conjugated esters

Abstract Indirect electrochemical oxidation of aliphatic ketones in methanol in an undivided cell in the presence of sodium iodide–sodium hydroxide system leads to the corresponding unsaturated esters as a result of the electrochemically induced Favorskii rearrangement of the primarily formed α , α -diiodoketones.

Indirect electrochemical oxidation of cyclic ketones: Strong influence of ring size on the result of the reaction

Abstract The result of the indirect electrochemical oxidation of cyclic ketones in methanol in the undivided cell in the presence of sodium iodide depends on the ring size. Cyclopentanone affords 2,2-dimethoxycyclopentanone. While cyclohexanone gives rise 2,2-dimethoxycyclo-hexanol, and cyclic ketones with higher ring size undergo new type of the electrochemically induced Favorskii rearrangement with the formation of methyl cycloalkencarboxylates containing in the ring on the one carbon atom less than starting ketone. So the simple electrocatalytic system can distinguish the ring size of cyclic ketones.

Electrochemical transformation of alkylidenemalonates into 2-alkyl-3,3-dimethoxyalkane-1,1-dicarboxylates via rearrangement

Abstract Alkylidenemalonates capable of migration of a double bond being electrolyzed in methanol in the presence of alkali metal halides in an undivided cell are transformed into 2-alkyl-3,3-dimethoxyalkane-1,1-dicarboxylates, acidification of which leads to 2-alkyl-3-oxoalkane-1,1-dicarboxylates.

Electrocatalytic transformation of dialkyl malonates and arylidene- or alkylidenemalononitriles into dialkyl esters of 3-substituted 2,2-dicyanocyclopropane-1,1-dicarboxylic acids

Electrolysis of alcoholic solutions of dialkyl malonates and arylidene- or alkylidenemalononitriles in the presence of NaBr in an undivided cell gave dialkyl esters of 3-substituted 2,2-dicyanocyclopropane-1,1-dicarboxylic acids in 60–90% yields.

ELECTROCHEMICAL TRANSFORMATION OF CYANOACETIC ESTER AND ALKYLIDENECYANOACETIC ESTERS INTO 3-SUBSTITUTED 1,2-DICYANOCYCLOPROPANE-1,2-DICARBOXYLATES

Electrolysis of cyanoacetic ester and alkylidenecyanoacetic esters in an undivided cell in the presence of mediators (alkali metal halides) gives rise to 3-substituted, 1,2-dicyanocyclopropane-1,2-dicarboxylates in 60–95% yields.